Insoluble polyanionic anthraquinones with two strong ionic O-K bonds as stable organic cathodes for pure organic K-ion batteries

一种新型不溶多阴离子有机正极材料在全有机钾离子电池中的应用

Abstract

A new organic cathode namely potassium 2,6-dihydroxyanthraquinone (AQ26OK, theoretical capacity (CT) = 169 mA h g−1) is synthesized and fully characterized for K-ion batteries. AQ26OK is called polyanionic organic cathode because it has a polyanionic organic skeleton (−2 valent) and two strong ionic K-O bonds. Consequently, the polyanionic AQ26OK is hardly soluble into most organic liquid electrolytes. In half cells (0.3–3.4 V vs. K+/K) using 1 mol L−1 KPF6 in dimethoxyethane, AQ26OK delivers a highly stable specific capacity of 201 mA h g−1@50 mA g−1 over 450 cycles (4-month test) and realizes ∼106 mA h g−1 for 3200 cycles at 500 mA g−1. Using the reduced state (K4TP) of potassium terephthalate (K2TP) as the organic anode, the resulting K4TP II AQ26OK organic potassium ion batteries can display a highly stable average discharge capacity of 135 mA h g−1cathode over 250 cycles at 100 mA g−1 and ∼47 mA h g−1 for 1000 cycles at 500 mA g−1 during the working voltage of 0.01–3.1 V. To the best of our knowledge, AQ26OK is among the best stable cathodes reported for K ion batteries.

摘要

有机小分子电极材料普遍会溶解在电解液中. 本文报道了一个新型有机小分子化合物蒽醌-2,6-二羟基钾(AQ26OK, 理论比容量:169 mA h g−1)作为钾离子电池的正极材料. AQ26OK在大π共轭蒽醌的基础上含有2个强的O-K离子键, 使得有机框架为−2价. 因此, AQ26OK可以称为多阴离子有机电极材料. AQ26OK在醚类电解液中基本不溶, 从而在钾离子电池中展现出较高的循环稳定性. 在半电池中(0.3–3.4 V), 使用1 mol L−1 KPF6 乙二醇二甲醚作为电解液, AQ26OK在50 mA g−1的小电流下可以达到201 mA h g−1的比容量, 且可以稳定循环超过450圈(寿命至少4个月); 其在大电流(500 mA g−1)下可以达到106 mA h g−1的比容量且循环3200圈. 在使用对苯二甲酸钾还原态(K4TP)作为有机负极的全有机钾离子电池中, 此K4TP IIAQ26OK有机钾离子电池(0.01–3.0 V)在小电流(100 mA g−1)下可以稳定循环超过250圈且平均放电比容量约为135 mA h g−1; 其在大电流(500 mA g−1)下循环1000圈的平均比容量约为47 mA h g−1. AQ26OK是目前钾离子电池有机正极中最稳定的材料之一.

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Acknowledgements

This work was supported by the Fundamental Research Funds of University of Electronic Science and Technology of China (UESTC, ZYGX2019J027), the Open Foundation of State Key Laboratory of Electronic Thin Films and Integrated Devices of UESTC (KFJJ201915), and Sichuan Science and Technology Program (20YYJC3821)

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Correspondence to Cong Fan 樊聪.

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Author contributions

Fan C conceived and supervised the research ideas; Hu J performed the experiments, organized the data and wrote the raw paper; Tang W, Liu S, Hu Y and Lai H carried out the characterizations; Yan Y and Xu L provided data curation All authors contributed to the general discussion

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The authors declare that they have no conflict of interest

Jiahui Hu is a master degree candidate at the School of Materials and Energy, University of Electronic Science and Technology of China (UESTC) under the supervision of Prof. Cong Fan. Her current research interests mainly focus on the design and synthesis of novel organic electrodes for Li/Na/K-ion batteries.

Cong Fan received his bachelor (2008) and PhD (2013) degrees in organic chemistry from Wuhan University. He is an associate professor at UESTC since August 2015. His current research interests are the skilled synthesis of organic electrode materials for rechargeable batteries.

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Hu, J., Tang, W., Liu, S. et al. Insoluble polyanionic anthraquinones with two strong ionic O-K bonds as stable organic cathodes for pure organic K-ion batteries. Sci. China Mater. (2021). https://doi.org/10.1007/s40843-020-1556-9

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Keywords

  • potassium 2,6-dihydroxyanthraquinone
  • insoluble organic cathodes
  • polyanionic character
  • ultra-stability
  • organic K-ion batteries